polymer material and its related chromophores supporting ... · singlet excited electronic states....

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Supporting Information

Optical characterization of a two-dimensional BODIPY-based

polymer material and its related chromophores

P. Piatkowski1,2, M. Moreno3, M. Liras4,5, F. Sánchez5 and A. Douhal1*

1 Departamento de Química Física, Facultad de Ciencias Ambientales y Bioquímica, and

Inamol, Universidad de Castilla-La Mancha, Avenida Carlos III, S.N., Toledo 45071,

Spain

2 Department of Chemistry, University of Warsaw, Żwirki i Wigury 101, 02-089

Warsaw, Poland

3Departament de Química, Universitat Autónoma de Barcelona, Bellaterra, 08193

Barcelona, Spain

4 IMDEA-Energía Parque Tecnológico de Móstoles Avda. Ramón de la Sagra, 3, 28935

Móstoles, Madrid, Spain

5Instituto de Química Orgánica General IQOG-CSIC Juan de la Cierva, 3 28006 Madrid

Spain

* Corresponding author: [email protected]

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2019

mailto:[email protected]

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Theoretical calculations

MD1. Optimization of the molecule in the ground electronic state reveals that the

system is almost planar and only two fluorine atoms and hydrogens of the methyl groups

are found symmetrically out the plane that contains the rest of the atoms. Therefore it

belongs to the C2v group of symmetry. Scheme S1 depicts the obtained geometry. The

full set of Cartesian Coordinates is given in the SI section.

A TDDFT calculation at the equilibrium geometry gives the energies of the lowest

singlet excited electronic states. The oscillator strengths between the ground and the

excited electronic states are also obtained. As those results give a direct measure of the

absorption intensity, a theoretical absorption spectrum of MD1 can be obtain (Scheme

S1).

Three active bands are predicted from the calculations (bands above 200 nm have

not been calculated as this high energy range has not been experimentally explored). The

most intensive one (571 nm, oscillator strength (f) 1.14) corresponds to the

HOMO→LUMO transition. The second, less intense band (f = 0.65), is predicted to peak

at 405 nm. This excitation mainly arises from the HOMO–2→LUMO transition. Finally

a third absorption band, almost as intense as the first one (f = 0.93), is found at 322 nm.

The main contribution to this excitation comes from the HOMO→LUMO+1 transition.

It has to be noted that the transition to the second excited electronic state (S2) peaking at

462 nm has small oscillator strength of 0.05 (Figure S2). The other two active bands

correspond to the excitation to the third (S3) and fourth (S4) excited states respectively.

At shorter wavelengths (higher energies) other states with small transition probabilities

are found. Among these S10 at 304 nm is the only one with a non-negligible oscillator

strength (f = 0.11). As seen in Figure S2 all these states are not making any relevant

contribution to the shape of the absorption spectrum. It is accepted that electronic states

3

with oscillator strength below 0.1 are “dark” states (i.e: states that cannot be accessed by

light irradiation of the ground electronic state).

The molecular orbitals implied in the allowed excitations are depicted in Figure

S3. It is clear that all orbitals are of π type. Obviously the most interesting transition is

the S0 to S1 as this one will mainly govern the photochemistry of MD1. Analysis of the

HOMO and LUMO states, the orbitals mainly implied in the S1 excitation, points to a

noticeable degree of internal charge transfer from the two lateral phenylacetylene rings

to the BODIPY central part of the molecule. Analysis of the Mulliken charges allows

quantifying this transfer: the total charge in the two phenylacetylene groups increases by

0.2378 u.a. upon S0 to S1 electronic excitation. The ulterior nuclear relaxation in S1

slightly increases this internal charge transfer up to 0.2750 a.u.

The optimized geometry in the S1 state does not noticeably differ from the one in

the ground state depicted in Figure S3. It maintains the C2v symmetry and only minor

differences in the bond distances are to be noted. The observed differences confirm the

change in bonding/antibonding character between the HOMO and LUMO for adjacent

atoms. The Cartesian Coordinates of this structure are given in the SI section. The final

energy of the structure gives a theoretical estimate of the main emission band of MD1

that is predicted to peak at 625 nm. The HOMO and LUMO, again the orbitals mainly

implied in the de-activation from S1 to S0, are also very similar to the ones depicted in

Figure S3.

Finally we have studied the rotation of the terminal phenyl groups in order to see

whether the two (equivalent) structures resulting from the rotation are freely

interconverting at room temperature. A reaction coordinate calculation reveals that the

maximum of energy along the phenyl rotation is at 90º (hardly a surprising fact) and that

the energy barrier for this rotation is very small, 1.00 kcal/mol, so that free rotation is

4

predicted at least in gas phase. The viscosity of the solvent, not considered in our

theoretical calculations could seriously hinder such a rotation.

MD2. Large MD2 molecular structure is a very symmetric one. Our calculations

at the ground electronic state confirm that this molecule belongs to the D3h symmetry

group (the three “branches” out of the central phenyl ring are equivalent). Scheme S2

depicts the theoretically calculated equilibrium geometry. The full Cartesian Coordinates

are to be found in the SI section.

At the equilibrium geometry in S0 the calculation of the lowest energy excited

electronic state reveals quite complicated pattern of excitations as some excited states are

now degenerate (as expected from the D3h symmetry group). In any case the absorption

spectra can be predicted from these results and the final shape is depicted in Figure S5.

Again, the transition to the first singlet excited electronic state S1 has the highest

probability. It peaks at 521 nm and has quite large oscillator strength of 1.38. Our results

also disclose that the S1 state is double degenerated. Disregarding the dark states, the next

allowed transition (f = 0.15) is found at 470 nm and it is also doubly degenerate. The

excited states accessed from this excitation are S7 and S8. The transitions form S0 to S3

and to S6 can be considered as dark states due to low oscillator strengths (less than 0.1).

Next bright states are two fully degenerate S10 and S11 states with f = 0.48 (401 nm). The

third almost degenerate state S12 also peaks at 401 nm but it has a smaller (f = 0.27)

transition probability. The next allowed transition is found at 372 nm. It corresponds to a

transition to a double degenerate state (S16 and S17) with modest activity (f = 0.22). The

last bright state in the relevant zone of the electromagnetic spectrum is found at 338 nm.

It is attributed to transitions from S0 to S23 and S24 (doubly degenerate) and it is one of

the most intensive bands (f=0.61). The energies of those last states are more prone to large

5

numerical errors as the theoretical calculation has included just 25 excited states. All other

states are dark states in the above described sense.

The analysis of the molecular orbitals implied in the electronic excitation is now

a quite complicated task. The largely extended π system of the molecule provokes that

the energy differences between adjacent orbitals are small and so the excitation pattern

that leads to a given excited state cannot be restricted to just one excitation (as done for

MD2 above). Additional complications in MD2 come from the high symmetry of the

molecule as now some orbitals are degenerate (this is the case of both the HOMO and the

LUMO). For instance, the most probable transition from S0 to S1 (and the degenerate S2)

has 14 excitations with coefficients higher than 0.1. A qualitative analysis of the

molecular orbitals involved in the transition in order to grasp the electronic rearrangement

upon excitation is therefore unattainable. Alternatively we will look at the charges in all

the atoms of the molecule in order to see relevant changes in the charge distributions upon

electronic excitation.

The optimization of MD2 in the S1 state does not apparently produce large

variations in the molecular geometry. However there are slight modifications of bond

distances that eventually break the whole symmetry of the molecule that only retains the

molecular plane of symmetry (CS). The most noticeable effect of the lowering in the

symmetry is that the molecular orbitals are no longer degenerate. Although, as the

deviations from the symmetric positions are tiny, there are very small energy differences

between the degenerate pairs of the excited states. This makes the analysis of the emission

spectrum, depicted in Figure S8, more complex. The lowest energy (highest wavelength)

transition to S1 is predicted to peak at 586 nm. It mainly involves the HOMO→LUMO

transition and is clearly allowed (f = 0.80), though it has not the highest probability as the

S0 → S2 transition, peaking at 529 nm has an oscillator strength of f = 0.91. S2 comes

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from a more complex pattern of excitation that mainly involves the HOMO→LUMO+1

excitation but with noticeable contributions of the HOMO-1 to both LUMO and

LUMO+2. A large number of other excitations with lower probabilities (0.13 < f < 0.27)

add up to a quite broad band that, according to the calculations, extends between 450 and

700 nm.

The second, high energy, band is seen in Figure S8 extending between 300 and

ca. 420 nm. It is also formed by several high and low-probability transitions. The most

intense ones peak at 407 nm (f = 0.70), 401 nm (f = 0.42), 348 nm (f = 0.68) and 340 nm

(f = 0.55). Excited states at higher energies (wavelength below 300 nm) have not been

calculated.

To have an idea of what electronic rearrangements are taking place upon

excitation to S1 we have analyzed the Mulliken atomic charges of the central phenyl ring

and the three acetylene groups that bond to the corresponding BODIPY units. There is a

noticeable charge transfer from the BODIPYs to the central part of the molecule that

amounts to 0.1495 a.u. without nuclear relaxation in the S1 state and to 0.2126 a.u.

between the S0 and S1 minimum energy geometries.

Finally we have also analyzed the internal rotation of MD2 in order to find

additional conformers in the ground electronic state. In that case there are three BODIPY

fragments that can rotate but just one additional rotamer different from the original one

that is obtained by rotation of just one BODIPY unit. As in the case of MD2, a reaction

coordinate calculation of the internal rotation of a BODIPY unit has been performed and

the obtained results show that the energy barrier for this internal rotation is very small

(1.21 kcal/mol) so that again free rotation is to be expected (at least in gas phase). Now

the rotamer obtained after 180 degrees rotation is not equivalent to the original one (as

one of the three BODIPY units points towards the reverse side) but the difference in

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energy between both rotamers is negligible (0.12 kcal/mol). We have also calculated the

absorption and emission electronic spectra of this additional equilibrium structure. Even

if now the ground electronic state geometry is no longer D3h and so there is no degeneracy

of the excited electronic states, the obtained results are almost identical to the ones of the

initial structure with differences between equivalent bands that never exceed 2 nm. The

only remarkable difference is that whereas otherwise degenerate bands appear almost at

the same wavelength (they differ by less than 2nm), the oscillator strengths may be now

quite disparate. However this difference has no repercussion on the predicted shape of the

electronic spectra that is virtually identical to the one depicted in Figure S8.

Table S1. Excitation energies of MD1 for different methods

6-31G(d,p) 6-31+G(d,p)E(eV) λ(nm) f E(eV) λ(nm) f Excitation

S1(opt.) 2.08 625 1.02 2.15 607 0.65 HLS1(FC) 2.17 571 1.14 2.26 548 0.78 HLS2 2.69 461 0.05 2.68 462 0.03 H-1LS3 3.06 405 0.65 3.14 394 0.75 H-2LS4 3.85 322 0.93 3.83 324 0.55 HL+1S5 3.90 318 0.00 3.87 320 0.00 H-3L

8

Table S2. Values of the maximum intensity wavelengths observed in the absorbance and

spectral shift of the emission maximum (pump = 490 nm) for MD1 in various solvents.

Table S3. Values of the dipole moments, polarity functions and viscosities of the solvents

used in the experiments

Table S4. Values of the quantum yield of MD1, MD2 and CMPBDP in different solvents.


spectral shift of the emission maximum (pump = 490 nm) for MD2 in various solvents.

Solvent Absorption Emission Shift abs (nm) em (nm) abs - em (cm-1)

DCM 562 595 1020ACN 557 593 1090

MeOH 555 593 1155TAC 557 593 1090

Solvent Dipol moment (D, 20 oC)

f(,n) Viscosity (cP, 25oC)

DCM 1.14 0.472 0.41ACN 3.44 0.711 0.34MeOH 2.87 0.711 0.54TAC 2.73 0.324 17.4

Solvent Quantum yield (%)MD2 MD1 CMPBDP

DCM 17 ± 4.3 36 ± 7.2 1.8 ± 0.72ACN 7 ± 2.1 25 ± 5 1.3 ± 0.68MeOH 11 ± 3 30 ± 9 1.5 ± 0.67TAC 37 ± 7.4 38 ± 7.4 -

Solvent Absorption Emission Shiftabs1 (nm) abs2 (nm) em1 (nm) em2 (nm) abs1 - em1

(cm-1)abs2 - em2

(cm-1)DCM 520 555 530 575 330 690ACN 515 545 525 570 300 840

MeOH 515 540 525 565 295 820TAC 520 550 525 570 295 700

CMPBDP

9


spectral shift of the emission maximum (pump = 490 nm) for CMPBDP in various

solvents.

Table S7. Values of fluorescence lifetimes (τi) and normalized (to 100) pre-exponential

factors (Ai) obtained from a global multiexponential fits of the emission decays of MD1

in DCM solution upon excitation at 371 and 470 nm.

Solvent Absorptionabs2 (nm)

Emissionem (nm)

DCMACN

MeOH

540515525

515520520

MD1 in DCMpump = 371 nm

obs (nm) A1/C1 (%)

1 (ns) A2/C2(%) 2 (ns) 2

545 6/1 0.52 94/99 3.7 1.09560 5/1 0.52 95/99 3.7 1.06580 5/1 0.52 95/99 3.7 1.04600 4/1 0.52 96/99 3.7 1.04640 5/1 0.52 95/99 3.7 1.01670 2/1 0.52 98/99 3.7 1.43

pump = 470 nm545 7/1 0.57 93/99 3.7 1.14560 5/1 0.57 95/99 3.7 1.02580 5/1 0.57 95/99 3.7 1.03600 5/1 0.57 95/99 3.7 1.10640 5/1 0.57 95/99 3.7 1.03670 5/1 0.57 95/99 3.7 1.03

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in ACN solution upon excitation at 371 and 470 nm.



in MeOH solution upon excitation at 371 and 470 nm.

MD1 in ACNpump = 371 nm

obs (nm) A1/C1 (%) 1 (ns) A2/C2(%) 2 (ns) 2

545 13/2 0.52 87/98 3.4 1.05560 13/2 0.52 87/98 3.4 1.14580 8/1 0.52 92/99 3.4 1.08600 8/1 0.52 92/99 3.4 1.09640 9/1 0.52 92/99 3.4 1.09670 9/1 0.52 91/99 3.4 1.06

pump = 470 nm545 12/2 0.51 88/98 3.4 1.11560 11/1 0.51 89/99 3.4 1.05580 9/1 0.51 95/99 3.4 1.11600 10/1 0.51 90/99 3.4 1.09640 11/2 0.51 90/98 3.4 1.11

MD1 in MeOHpump = 371 nm

obs (nm) A1/C1 (%)

1 (ns) A2/C2 (%) 2 (ns) 2

545 7/1 0.57 93/99 3.2 1.14560 5/1 0.57 95/99 3.2 1.02580 5/1 0.57 95/99 3.2 1.03600 5/1 0.57 95/99 3.2 1.10640 5/1 0.57 95/99 3.2 1.03670 5/1 0.57 95/99 3.2 1.03

pump= 470 nm545 2/2 0.52 98/98 3.2 1.16560 2/2 0.52 98/98 3.2 1.05580 5/1 0.52 95/99 3.2 1.10600 5/1 0.52 95/99 3.2 1.06640 6/1 0.52 94/99 3.2 1.07670 5/2 0.52 95/98 3.2 1.15

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in TAC solvent upon excitation at 371 nm.



in DCM solution upon excitation at 371 and 470 nm.

MD1 in TACpump = 371 nm

obs(nm) A1/C1 (%)

1 (ns) A2/C2(%) 2 (ns) A3/C3(%) 3 (ns) 2

545 57/4 0.11 6/5 1.1 37/91 3.8 1.18560 44/2 0.11 5/2 1.1 51/96 3.7 1.06580 19/1 0.16 4/2 1.1 77/97 3.7 1.04600 - 0.19 5/1 1.2 95/99 3.9 1.09640 - - 5/1 1.1 95/99 3.5 1.08670 - - 5/2 1.1 95/98 3.5 1.05


545 47/4 0.12 19/22 1.2 34/74 3.8 1.03560 47/3 0.12 19/22 1.3 33/75 3.8 1.12580 30/2 0.14 19/15 1.5 51/83 3.5 1.14600 - - 5/3 1.1 92/97 4.0 1.09640 - - 6/3 1.1 94/97 3.9 1.14670 - - 5/3 1.1 95/97 3.9 1.19

MD2 in DCMpump = 371 nm

obs (nm) A1/C1 (%) 1 (ns) A2/C2 (%) 2 (ns) A3/C3 (%) 3 (ns) 2

525 10/1 0.11 16/5 1.0 74/94 4.8 1.11550 13/1 0.11 10/3 0.9 74/96 3.7 1.06560 14/1 0.11 5/2 1.0 81/97 3.6 1.06580 11/1 0.11 5/1 1.2 84/98 3.6 1.02590 13/1 0.21 5/2 1.1 82/97 3.6 1.07620 14/1 0.12 5/2 1.1 81/97 3.6 1.03

pump = 470 nm 525 38/2 0.10 13/6 1.1 49/92 4.5 1.15550 35/1 0.10 11/5 1.1 54/94 3.8 1.02560 13/1 0.13 8/3 1.1 79/96 3.7 1.01575 9/1 0.12 6/2 0.9 85/97 3.6 1.06600 10/1 0.13 6/2 0.8 84/97 3.8 1.09620 13/1 0.13 5/2 0.9 82/97 3.6 1.10

12



in ACN solution upon excitation at 371 and 470 nm.



in MeOH solution upon excitation at 371 and 470 nm.

MD2 in ACNpump = 371 nm

obs (nm) A1/C1 (%) 1 (ns) A2/C2 (%) 2 (ns)

A3/C3 (%) 3 (ns) 2

525 8/1 0.12 22/4 0.8 70/95 5.5 1.04550 11/1 0.12 66/32 0.8 23/67 4.4 1.06560 12/1 0.12 82/70 0.8 6/29 4.2 1.05575 8/1 0.12 89/89 0.8 3/10 2.7 1.18600 9/1 0.12 88/89 0.8 3/10 2.6 1.01620 8/1 0.12 88/88 0.8 4/11 2.4 1.02

pump = 470 nm525 13/1 0.12 33/9 0.8 54/90 4.8 1.07550 22/2 0.12 54/36 1.0 24/62 4.0 1.02560 22/2 0.12 62/50 1.0 16/48 3.6 1.06575 22/2 0.12 64/55 1.0 14/43 3.4 1.03600 24/3 0.14 62/53 0.9 14/44 3.3 1.09620 23/3 0.12 60/50 0.9 17/47 3.3 1.03

MD2 in MeOH, pump = 371 nm


515 12/1 0.10 10/2 0.8 78/97 5.4 1.08525 11/1 0.12 15/3 0.8 74/96 5.5 1.07545 7/1 0.14 2/1 0.8 91/98 3.2 1.02560 7/1 0.17 - - 93/99 3.2 1.08620 8/1 0.17 - - 92/99 3.2 1.10

pump = 470 nm525 8/1 0.11 10/2 0.8 82/97 5.4 1.06550 32/2 0.10 29/13 1.0 39/85 4.7 1.04560 29/2 0.13 37/23 1.0 34/75 4.2 1.09575 30/2 0.10 38/26 1.1 32/72 4.2 1.16600 31/2 0.11 39/27 1.1 30/71 3.5 1.13620 30/2 0.12 40/31 1.1 30/67 3.5 1.03

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in TAC solution upon excitation at 371 nm.


factors (Ai) obtained from a global multiexpon0.80.8ential fits of the emission decays of

CMPBDP in DCM suspension upon excitation at 371.



525 37/2 0.15 15/5 1.3 48/93 4.9 1.08550 27/2 0.16 14/5 1.3 59/93 3.6 1.02560 16/1 0.18 9/3 1.3 75/96 3.5 1.07575 - - 5/2 1.3 95/98 3.5 1.08600 - - 5/2 1.3 95/98 3.5 1.08620 - - 5/2 1.3 95/98 3.5 1.06

pump = 470 nm 525 16/1 0.15 14/5 1.3 70/94 5.0 1.08550 28/2 0.20 17/8 1.3 54/90 4.5 1.22560 19/1 0.14 9/4 1.3 72/95 3.8 1.04575 - - 6/2 1.3 94/98 3.7 1.08600 - - 7/2 1.3 93/98 3.7 1.06620 - - 7/2 1.3 93/98 3.7 1.10

CMPBDP in DCMpump = 371 nm

obs (nm) A1/C1 (%) 1 (ns) A2/C2 (%) 2 (ns) A3/C3 (%) 3(ns) 2

500 38/5 0.22 29/12 0.7 33/83 4.3 1.05530 40/5 0.22 22/8 0.7 39/87 4.2 1.05560 24/5 0.22 60/44 0.7 16/51 3.1 1.13590 16/3 0.22 56/35 0.7 28/62 2.8 1.05600 17/3 0.22 54/33 0.7 29/64 2.8 1.04650 20/4 0.22 53/34 0.7 27/61 2.8 1.04

14


factors (Ai) obtained from a global multiexponential fits of the emission decays of

CMPBDP in ACN suspension upon excitation at 371 nm.


factors (Ai) obtained from a global multiexponential fits of the emission decays of

CMPBDP in MeOH suspension upon excitation at 371.

CMPBDP in ACNpump = 371 nm

obs(nm) A1/C1 (%) 1 (ns) A2/C2 (%) 2 (ns) A3/C3 (%) 3 (ns) 2

500 68/6 0.08 18/17 0.6 13/77 3.9 1.09525 58/4 0.09 25/15 0.5 17/81 4.0 1.11560 58/4 0.08 26/16 0.5 16/80 3.5 1.01600 64/5 0.09 25/25 0.5 11/70 3.4 1.10620 66/6 0.08 25/27 0.5 9/67 3.4 1.03

CMPBDP in MeOHpump= 371 nm

obs(nm) A1/C1 (%) 1 (ns) A2/C2 (%) 2 (ns) A3/C3 (%) 3 (ns) 2

500 50/4 0.11 22/12 0.8 28/84 4.2 1.09530 50/4 0.11 27/14 0.6 23/82 4.3 1.11560 34/4 0.11 48/27 0.6 18/69 3.8 1.01590 36/4 0.11 48/32 0.6 16/64 3.4 1.10620 76/11 0.11 19/31 0.5 5/58 3.3 1.03650 80/15 0.11 16/31 0.5 4/54 3.2 1.10

15

Table S18. Values of time constants (τi) and normalized (to 100) pre-exponential factors

(Ai) of the multiexponential functions used to fit the fs-emission signals of MD1 in DCM

upon excitation at 505 nm.


(Ai) of the multiexponential functions used to fit the fs-emission signals of MD1 in ACN



(Ai) of the multiexponential functions used to fit the fs-emission signals of MD1 in

MeOH upon excitation at 505 nm.

MD1 in DCMem (nm) 1 (ps) A1 (%) 2 (%) A2 (%) Offset (%)

545 0.4 51 2 31 18560 0.4 45 2 30 25575 0.3 18 2 29 53600 0.4 (-) 8 3 (-) 2 90630 0.3 (-) 11 2 (-) 10 79670 0.4 (-) 11 2 (-) 14 75

MD1 in ACNem (nm) 1 (ps) A1 (%) 2 (%) A2 (%) Offset (%)

545 0.3 70 2 18 12560 0.3 44 2 26 30575 0.4 20 2 17 63600 0.4 (-) 10 2 (-) 4 86630 0.4 (-) 16 2 (-) 6 78670 0.4 (-) 23 3 (-) 4 76

MD1 in MeOHem (nm) 1 (ps) A1 (%) 2 (%) A2 (%) Offset (%)

545 0.4 38 7 23 39560 0.4 24 7 21 55575 0.4 15 7 20 65600 0.4 (-) 16 - - 84630 0.4 (-) 15 5 (-) 2 83670 0.4 (-) 17 6 (-) 2 81

16


(Ai) of the multiexponential functions used to fit the fs-emission signals of MD1 in TAC



(Ai) of the multiexponential functions used to fit the fs-emission signals of MD2 in DCM



(Ai) of the multiexponential functions used to fit the fs-emission signals of MD2 in ACN


MD1 in TACem (nm) 1 (ps) A1 (%) 2 (%) A2 (%) Offset (%)

545 0.4 42 7 24 34560 0.4 27 7 21 52575 - - 5 10 90600 0.4 (-) 10 6 (-) 6 84630 0.4 (-) 10 6 (-) 3 84670 0.4 (-) 9 7 (-) 11 80

MD2 in DCMem (nm) 1 (ps) A1 (%) 2 (%) A2 (%) 3 (%) A3 (%) Offset (%)

530 0.3 68 4 15 - - 17545 0.3 53 3 20 - - 27560 0.4 28 4 16 - - 56575 - - 3 9 - - 91600 0.4 (-) 6 3 (-) 1 - - 96650 - - 3 (-) 38 3 37 25

MD2 in ACNem (nm) 1 (ps) A1 (%) 2 (%) A2 (%) Offset (%)

530 0.3 65 4 13 22545 0.3 56 5 14 30560 0.3 10 5 30 60575 0.3 13 - - 87600 - - 4 6 94650 0.3 (-) 12 - - 88

17


(Ai) of the multiexponential functions used to fit the fs-emission signals of MD2 in

MeOH upon excitation at 505 nm.


(Ai) of the multiexponential functions used to fit the fs-emission signals of MD2 in TAC


MD2 in MeOHem (nm) 1 (ps) A1 (%) 2 (%) A2 (%) Offset (%)

530 0.3 18 13 20 62545 0.3 13 11 22 71560 0.3 12 13 20 74575 - - 7 14 86600 - - 7 13 87650 0.3 (-) 9 7 10 81

MD2 in TACem (nm) 1 (ps) A1 (%) 2 (%) A2 (%) Offset (%)

530 0.3 48 6 12 40545 0.3 37 8 16 47560 0.3 16 6 7 77575 - - - - 100600 0.3 17 6 3 80650 0.3 (-) 12 - - 88

18

Scheme S1: Synthesis of MD1.

Scheme S2: Synthesis of MD2.

Scheme S3: Synthesis of CMPBDP.

19

Scheme S4: Equilibrium geometry of MD1 at S0.

Scheme S5: Equilibrium geometry of MD2 at S0.

20

350 400 450 500 550 6000.0

0.5

1.0

Excitation (normalized to 1)A

bsor

banc

e (n

orm

aliz

ed to

1)

Absorbance Excitation

Wavelength / nm

(a)

350 400 450 500 550 6000.0

0.5

1.0

A

bsor

banc

e (n

orm

aliz

ed to

1)

Absorbance Exciataion

Wavelegth / nm

(b)

Excitation (normalized to 1)

300 350 400 450 500 550 6000.0

0.5

1.0 Excitation (norm

alized to 1) Absorbance Excitation

Abs

orba

nce

(nor

mal

ized

to 1

)

Wavelegth / nm

(c)

350 400 450 500 550 6000.0

0.5

1.0

Absorbance Excitation

Abso

rban

ce (n

orm

aliz

ed to

1)

Wavelength / nm

(d)


Figure S1. Normalized (to 1) absorption (black solid line) and excitation (red dashed line)

spectra of MD1 in (a) DCM, (b) ACN, (c) MeOH, (d) TAC. The excitation spectra were

observed at 650 nm.

Figure S2: Absorption spectrum of MD1. Vertical blue lines indicate the exact position

of the excitation energy and the oscillator strength whereas the bands are drawn assuming

a standard Gaussian shape.

21

Figure S3: Molecular orbitals of MD1 involved in the allowed electronic transitions.

550 600 650 7000.0

0.5

1.0

DCM ACN MeOH TAC

Emis

sion

/ a.

u.

Wavelegth / nm

Figure S4. Normalized (to the maximum of intensity) emission spectra of MD1 in DCM

(black solid line), ACN (red dashed line), MeOH (blue dashed dotted line), TAC (green

solid line) upon excitation at 370 nm.

22

Figure S5: Absorption spectrum of MD2. Vertical blue lines indicate the exact position

of the excitation energy and the calculated oscillator strength whereas the bands are

shaped assuming a standard Gaussian shape.

500 550 600 650 7000.0

0.5

1.0

ex = 370 nm

DCM ACN MeOH TAC

Emis

sion

/ a.

u.

Wavelegth / nm

Figure S6. Normalized (to the maximum of intensity) emission spectra of MD2 in DCM

(black solid line), MeOH (red dashed line), ACN (blue dashed dotted line), TAC (green

solid line) upon excitation at 370 nm.

23

350 400 450 500 550 6000.0

0.5

1.0

Absorbance em = 540 nm em = 630 nm

Abs

orba

nce

(nor

mal

ized

to 1

)

Wavelegth / nm

(a)


350 400 450 500 550 6000.0

0.5

1.0


Wavelength / nm

(b)


Abs

orba

nce

(nor

mal

ized

to 1

)

350 400 450 500 550 6000.0

0.5

1.0


Wavelegth / nm

(c)

Abs

orba

nce

(nor

mal

ized

to 1

) Excitation (normalized to 1)

350 400 450 500 550 6000.0

0.5

1.0


Wavelength / nm

(d) Excitation (normalized to 1)

Abso

rban

ce (n

orm

aliz

ed to

1)

Figure S7. Normalized to 1 absorption (black solid line) and excitation (red dashed line

and blue dashed dotted line) spectra of MD2 in (a) DCM, (b) ACN, (c) MeOH and (d)

TAC. Observation wavelengths for excitation spectra are indicated in the inset.

Figure S8: Emission spectrum of MD2. Vertical blue lines indicate the exact position of

the excitation energy and the calculated oscillator strength whereas the bands are shaped

assuming a standard Gaussian shape.

24

400 500 600 700 8000.0

0.5

1.0


Wavelegth / nm

(a)A

bsor

banc

e (n

orm

aliz

ed to

1) Excitation (norm

alized to 1)

400 500 600 700 8000.0

0.5

1.0 Absorbance em = 550 nm em = 650 nm

(b)

Wavelegth / nm

Abs

orba

nce

(nor

mal

ized

to 1

) Excitation (normalized to 1)

400 500 600 700 8000.0

0.5

1.0


Wavelegth / nm

(c)


Abs

orba

nce

(nor

mal

ized

to 1

)

Figure S9. Normalized (to the maximum of intensity) absorption (black solid line) and

excitation (red dashed line and blue dashed dotted line) spectra of CMPBDP in (a) DCM,

(b) MeOH and (c) ACN. Observation wavelengths for excitation spectra are indicated in

the inset.

450 500 550 600 650 7000.0

0.5

1.0

ex = 370 nm

DCM MeOH ACN

Emis

sion

/a.u

.

Wavelegth / nm

Figure S10. Normalized emission spectra of CMPBDP in DCM (black solid line), ACN

(red dashed line), MeOH (blue solid line) excitation at 370 nm.

25

0 3 6 9 12 150.0

0.5

1.0

1.5

(4)(3)(2)(1)

pump = 470 nmEm

issi

on /

a.u.

Time / ns

(a)

0 5 10 150.0

0.5

1.0

1.5

(b)

(4)(3)(2)

(1)

Time / ns

Emis

sion

/ a.

u.

pump = 470 nm

Figure S11. Normalized to 1 magic-angle emission decays of (a) MD1 and (b) MD2 in

various solvents (1) TAC, (2) DCM, (3) MeOH, (4) ACN. The excitation and observation

wavelengths for all samples were at 470 and 560 nm, respectively. The solid lines are

from the best multiexponential fits to the experimental data. For clarity, the TA decay

signal was offset on the y axis.

26

550 600 650 7000.0

0.5

1.0(a)

1×10-6 M 5×10-5 M

Emis

sion

/ a.

u.

Wavelegth / nm

500 550 600 650 7000.0

0.5

1.0

1×10-6 M 5×10-5 M

Emis

sion

/ a.

u.

Wavelegth / nm

(b)

Figure S12. Normalized (to the maximum of intensity) emission spectra of (a) MD1 and

(b) MD2 in MeOH at two concentrations (inset). The excitation wavelength for both

samples was 470 nm.

27

0 5 10 150.0

0.5

1.0

1×10-6 M

5×10-5 M

obs = 545 nm

Fluo

resc

ence

/ a.

u.

Time / ps

(a)

0 5 10 150.0

0.5

1.0

5×10-5 M

1×10-6 M

obs = 580 nm

Time / ps

Fluo

resc

ence

/ a.

u.

(b)

0 5 10 150.0

0.5

1.0(c)

5×10-5 M

1×10-6 M

obs = 600 nm

Time / ps

Fluo

resc

ence

/ a.

u.

Figure S13. Normalized emission decays of MD1 in MeOH solution, at two

concentrations (inset), upon excitation at 470 nm and observing at (a) 545 nm, (b) 560

nm and (c) 600 nm.

28

0 5 10 150.0

0.5

1.0

2.5×10-5 M

Fluo

resc

ence

/ a.

u.

Time / ps

obs = 525 nm

1×10-6 M

(a)

0 5 10 150.0

0.5

1.0

1×10-6 M2.5×10-5 M

obs = 560 nm(b)

Time / ps

Fluo

resc

ence

/ a.

u.

0 5 10 150.0

0.5

1.0

(c)

1×10-6 M

2.5×10-5 M

obs = 600 nm

Time / ps

Fluo

resc

ence

/ a.

u.

Figure S14. Normalized emission decays of MD2 in MeOH solution, at two

concentrations (inset), upon excitation at 470 nm and observing at (a) 545 nm, (b) 560

nm and (c) 600 nm.

29

Cartesian coordiantes (in Å) in ground state of MD1

1 6 -0.858270 0.006280 1.216641

2 6 -1.531914 0.001201 0.000000

3 6 -0.858270 0.006280 -1.216641

4 6 0.933922 0.011460 2.538901

5 6 -0.220717 0.007200 3.381053

6 6 -1.352355 0.003798 2.545268

7 1 -2.616275 -0.006288 0.000000

8 6 -1.352355 0.003798 -2.545268

9 6 0.933922 0.011460 -2.538901

10 6 -0.220717 0.007200 -3.381053

11 7 0.542988 0.011732 1.253819

12 7 0.542988 0.011732 -1.253819

13 5 1.477104 0.008190 0.000000

14 9 2.278399 1.149830 0.000000

15 9 2.270673 -1.138864 0.000000

16 6 -2.783162 0.022294 -2.975325

17 1 -3.434925 -0.467690 -2.247249

18 1 -3.144365 1.050372 -3.102543

19 1 -2.901032 -0.483022 -3.937577

20 6 -2.783162 0.022294 2.975325

21 1 -3.144365 1.050372 3.102543

22 1 -3.434925 -0.467690 2.247249

23 1 -2.901032 -0.483022 3.937577

24 6 2.364064 0.010600 2.956817

25 1 2.877007 -0.871163 2.560504

26 1 2.880024 0.887654 2.554283

27 1 2.440411 0.014056 4.044694

28 6 2.364064 0.010600 -2.956817

29 1 2.880024 0.887654 -2.554283

30 1 2.877007 -0.871163 -2.560504

31 1 2.440411 0.014056 -4.044694

30

32 6 -0.201485 0.002125 -4.794026

33 6 -0.201485 0.002125 4.794026

34 6 -0.191417 -0.003906 -6.012416

35 6 -0.191417 -0.003906 6.012416

36 6 -0.179964 -0.009788 -7.437523

37 6 1.040029 -0.010463 -8.145488

38 6 -1.389061 -0.014935 -8.163974

39 6 1.044797 -0.015779 -9.537832

40 1 1.974282 -0.006675 -7.593466

41 6 -1.372789 -0.020526 -9.556217

42 1 -2.331491 -0.014743 -7.626014

43 6 -0.158653 -0.020894 -10.248488

44 1 1.991125 -0.016132 -10.070354

45 1 -2.310918 -0.024598 -10.103056

46 1 -0.150366 -0.025255 -11.334118

47 6 -0.179964 -0.009788 7.437523

48 6 -1.389061 -0.014935 8.163974

49 6 1.040029 -0.010463 8.145488

50 6 -1.372789 -0.020526 9.556217

51 1 -2.331491 -0.014743 7.626014

52 6 1.044797 -0.015779 9.537832

53 1 1.974282 -0.006675 7.593466

54 6 -0.158653 -0.020894 10.248488

55 1 -2.310918 -0.024598 10.103056

56 1 1.991125 -0.016132 10.070354

57 1 -0.150366 -0.025255 11.334118

Cartesian coordiantes (in Å) in first singlet excited state of MD1

1 6 -0.911635 0.017719 1.223074

2 6 -1.605657 0.021306 0.000000

3 6 -0.911635 0.017719 -1.223074

31

4 6 0.922070 0.016544 2.527243

5 6 -0.224167 0.013357 3.377552

6 6 -1.386262 0.012556 2.540194

7 1 -2.687534 0.026545 0.000000

8 6 -1.386262 0.012556 -2.540194

9 6 0.922070 0.016544 -2.527243

10 6 -0.224167 0.013357 -3.377552

11 7 0.505912 0.018698 1.246941

12 7 0.505912 0.018698 -1.246941

13 5 1.431493 0.017268 0.000000

14 9 2.244521 1.158998 0.000000

15 9 2.241138 -1.126799 0.000000

16 6 -2.811943 0.028116 -2.988614

17 1 -3.453260 -0.544916 -2.311663

18 1 -3.216262 1.048127 -3.033701

19 1 -2.908197 -0.401600 -3.989725

20 6 -2.811943 0.028116 2.988614

21 1 -3.216262 1.048127 3.033701

22 1 -3.453260 -0.544916 2.311663

23 1 -2.908197 -0.401600 3.989725

24 6 2.357554 0.013124 2.922256

25 1 2.866382 -0.868903 2.518577

26 1 2.872351 0.887916 2.510720

27 1 2.452698 0.017379 4.009043

28 6 2.357554 0.013124 -2.922256

29 1 2.872351 0.887916 -2.510720

30 1 2.866382 -0.868903 -2.518577

31 1 2.452698 0.017379 -4.009043

32 6 -0.189000 0.004024 -4.771337

33 6 -0.189000 0.004024 4.771337

34 6 -0.173196 -0.005639 -5.998370

35 6 -0.173196 -0.005639 5.998370

32

36 6 -0.150762 -0.016362 -7.409682

37 6 1.080079 -0.018241 -8.110593

38 6 -1.359555 -0.025521 -8.147943

39 6 1.093490 -0.028844 -9.499680

40 1 2.008499 -0.011314 -7.549533

41 6 -1.330621 -0.036156 -9.536788

42 1 -2.304601 -0.024251 -7.615312

43 6 -0.107843 -0.037845 -10.218094

44 1 2.041926 -0.030211 -10.027729

45 1 -2.262459 -0.043201 -10.093565

46 1 -0.091176 -0.046169 -11.303410

47 6 -0.150762 -0.016362 7.409682

48 6 -1.359555 -0.025521 8.147943

49 6 1.080079 -0.018241 8.110593

50 6 -1.330621 -0.036156 9.536788

51 1 -2.304601 -0.024251 7.615312

52 6 1.093490 -0.028844 9.499680

53 1 2.008499 -0.011314 7.549533

54 6 -0.107843 -0.037845 10.218094

55 1 -2.262459 -0.043201 10.093565

56 1 2.041926 -0.030211 10.027729

57 1 -0.091176 -0.046169 11.303410

Cartesian coordiantes (in Å) in ground state of MD2

1 6 -7.026246 7.238235 0.119943

2 6 -5.677000 6.931126 0.082814

3 6 -5.217119 5.611617 0.086483

4 6 -9.203873 6.807805 0.202352

5 6 -9.064256 8.225525 0.168081

6 6 -7.697188 8.498636 0.116527

7 1 -4.953795 7.738153 0.045364

33

8 6 -3.904100 5.092000 0.046970

9 6 -5.433624 3.394091 0.128505

10 6 -4.040642 3.687419 0.074341

11 7 -7.987984 6.224770 0.174718

12 7 -6.126402 4.547898 0.134282

13 5 -7.681294 4.695866 0.195062

14 9 -8.165575 4.121547 1.373943

15 9 -8.263448 4.075231 -0.911835

16 6 -2.623607 5.858839 -0.025018

17 1 -2.141227 5.727258 -1.000851

18 1 -2.776376 6.929073 0.130074

19 1 -1.914652 5.503668 0.730099

20 6 -7.036435 9.840617 0.048022

21 1 -5.990233 9.796873 0.360915

22 1 -7.058397 10.243872 -0.971646

23 1 -7.546403 10.565080 0.690341

24 6 -10.461563 6.004663 0.253811

25 1 -10.621508 5.482194 -0.695756

26 1 -10.392457 5.239150 1.031116

27 1 -11.326695 6.639373 0.449736

28 6 -6.082843 2.052949 0.175512

29 1 -6.680398 1.948029 1.086326

30 1 -6.766238 1.928993 -0.670014

31 1 -5.328367 1.265691 0.147973

32 6 -2.999347 2.732674 0.054394

33 6 -2.094403 1.917323 0.037485

34 6 9.795203 2.429428 -0.071412

35 6 8.844749 1.423495 -0.040400

36 6 7.474613 1.698153 -0.051454

37 6 10.531079 4.524009 -0.146679

38 6 11.681169 3.683341 -0.113333

39 6 11.221766 2.366952 -0.064317

34

40 1 9.171294 0.390121 -0.004216

41 6 6.359551 0.831335 -0.024403

42 6 5.675041 3.011872 -0.095403

43 6 5.219397 1.663049 -0.052087

44 7 9.411121 3.772915 -0.123226

45 7 7.020889 3.022139 -0.094065

46 5 7.938632 4.286148 -0.146079

47 9 7.696347 5.099280 0.962504

48 9 7.693936 4.999091 -1.323544

49 6 6.367817 -0.662398 0.015271

50 1 5.952372 -1.081254 -0.908720

51 1 7.375076 -1.064930 0.141782

52 1 5.748144 -1.033662 0.838480

53 6 12.042379 1.116197 0.000457

54 1 12.402119 0.927322 1.019106

55 1 11.473092 0.238308 -0.314833

56 1 12.924823 1.189533 -0.642552

57 6 10.478168 6.015416 -0.194025

58 1 9.772587 6.346835 -0.960230

59 1 10.124757 6.417053 0.762097

60 1 11.461708 6.437780 -0.403795

61 6 4.850126 4.253019 -0.138711

62 1 5.077446 4.894720 0.718091

63 1 5.076773 4.831958 -1.039298

64 1 3.788553 4.002602 -0.129702

65 6 3.868122 1.250611 -0.040239

66 6 2.707049 0.882079 -0.030030

67 6 -2.782009 -9.674538 -0.106394

68 6 -3.180550 -8.349361 -0.072498

69 6 -2.259778 -7.298248 -0.077281

70 6 -1.332598 -11.356048 -0.182897

71 6 -2.634559 -11.934309 -0.153525

35

72 6 -3.546969 -10.880236 -0.103481

73 1 -4.239326 -8.117889 -0.040455

74 6 -2.456370 -5.899693 -0.046314

75 6 -0.224281 -6.391934 -0.110131

76 6 -1.167305 -5.325152 -0.066743

77 7 -1.425683 -10.010805 -0.155572

78 7 -0.885620 -7.564059 -0.116418

79 5 -0.246773 -8.989652 -0.168827

80 9 0.571920 -9.187813 0.944466

81 9 0.500904 -9.129567 -1.341782

82 6 -3.756281 -5.163499 -0.011194

83 1 -3.917088 -4.607034 -0.942023

84 1 -4.605759 -5.835675 0.127291

85 1 -3.767019 -4.430704 0.802576

86 6 -5.040325 -10.969801 -0.041460

87 1 -5.383131 -11.218033 0.970273

88 1 -5.517913 -10.029911 -0.328745

89 1 -5.416570 -11.752124 -0.707953

90 6 -0.013407 -12.053861 -0.228195

91 1 0.627431 -11.606839 -0.992569

92 1 0.508634 -11.948368 0.729205

93 1 -0.137142 -13.116933 -0.439041

94 6 1.262834 -6.294527 -0.145845

95 1 1.701717 -6.814975 0.710894

96 1 1.656459 -6.775360 -1.046689

97 1 1.574181 -5.249243 -0.130594

98 6 -0.851530 -3.948172 -0.047590

99 6 -0.590985 -2.758258 -0.032019

100 6 0.302720 1.384936 0.003208

101 6 1.349662 0.446179 -0.017991

102 6 1.046974 -0.927296 -0.027967

103 6 -0.289574 -1.364869 -0.017665

36

104 6 -1.327449 -0.416012 0.004249

105 6 -1.038001 0.960176 0.014888

106 1 0.530748 2.444432 0.011178

107 1 1.850609 -1.654291 -0.045082

108 1 -2.359042 -0.748297 0.012333

109 6 -10.191835 9.221093 0.157333

110 1 -11.009812 8.861981 0.792767

111 1 -9.847939 10.157475 0.611147

112 6 -10.739406 9.516702 -1.251568

113 1 -11.130367 8.608868 -1.722091

114 1 -11.550508 10.250664 -1.207052

115 1 -9.954993 9.916528 -1.901925

116 6 -2.944495 -13.406241 -0.146597

117 1 -2.223282 -13.939779 -0.776643

118 1 -3.924868 -13.568787 -0.608718

119 6 -2.942485 -14.029956 1.261658

120 1 -3.180110 -15.097570 1.213821

121 1 -1.963585 -13.922295 1.739600

122 1 -3.682487 -13.545924 1.906864

123 6 13.111546 4.148871 -0.103158

124 1 13.742600 3.379880 -0.563083

125 1 13.216057 5.039418 -0.733838

126 6 13.647951 4.463247 1.305988

127 1 13.596391 3.581288 1.952183

128 1 14.691893 4.789830 1.260130

129 1 13.065496 5.258502 1.782155

37

Cartesian coordiantes (in Å) in first singlet excited state of MD2

1 6 5.171406 -8.632844 0.159667

2 6 3.925527 -8.033257 0.140994

3 6 3.772348 -6.643240 0.109511

4 6 7.391075 -8.700191 0.180691

5 6 6.936351 -10.051826 0.198295

6 6 5.543291 -10.012575 0.184903

7 1 3.039109 -8.657698 0.146565

8 6 2.609098 -5.845408 0.082824

9 6 4.482757 -4.530865 0.068506

10 6 3.058165 -4.505902 0.056536

11 7 6.337438 -7.860025 0.158214

12 7 4.898006 -5.809805 0.099550

13 5 6.382054 -6.301054 0.127480

14 9 7.018531 -5.812399 1.271491

15 9 7.050764 -5.862639 -1.016401

16 6 1.188032 -6.306563 0.072408

17 1 0.707738 -6.076474 -0.885880

18 1 1.105298 -7.382737 0.238270

19 1 0.608073 -5.797700 0.849474

20 6 4.597094 -11.172818 0.177746

21 1 3.601749 -10.889726 0.528894

22 1 4.484687 -11.588683 -0.830835

23 1 4.960176 -11.981282 0.819483

24 6 8.797971 -8.201515 0.177865

25 1 9.048004 -7.768503 -0.796996

26 1 8.923358 -7.409826 0.921066

27 1 9.500933 -9.008277 0.388676

28 6 5.417531 -3.369933 0.052553

29 1 6.054803 -3.379567 0.942092

30 1 6.081451 -3.425917 -0.815475

31 1 4.859266 -2.433432 0.019703

38

32 6 2.257963 -3.344540 0.025228

33 6 1.556385 -2.348589 -0.000906

34 6 -10.101711 -0.105204 -0.148161

35 6 -8.970340 0.695955 -0.183159

36 6 -7.665317 0.114589 -0.143868

37 6 -11.275914 -2.011536 -0.052655

38 6 -12.213816 -0.947986 -0.119631

39 6 -11.486884 0.249321 -0.179629

40 1 -9.070483 1.771680 -0.240002

41 6 -6.412046 0.693247 -0.166009

42 6 -6.221914 -1.620122 -0.045022

43 6 -5.465476 -0.414055 -0.102502

44 7 -10.010658 -1.504966 -0.070973

45 7 -7.525471 -1.298078 -0.069233

46 5 -8.706520 -2.319804 -0.016648

47 9 -8.625898 -3.063428 1.171680

48 9 -8.612541 -3.195719 -1.110881

49 6 -6.054493 2.140789 -0.240265

50 1 -5.464441 2.361914 -1.138130

51 1 -6.945072 2.772642 -0.262775

52 1 -5.448011 2.447296 0.620623

53 6 -12.006470 1.651709 -0.250829

54 1 -11.900213 2.180412 0.706216

55 1 -11.468570 2.243722 -1.000683

56 1 -13.067386 1.670299 -0.514060

57 6 -11.528489 -3.479538 0.027981

58 1 -11.027418 -4.006195 -0.792300

59 1 -11.119090 -3.895324 0.956470

60 1 -12.596700 -3.698868 -0.011160

61 6 -5.717835 -3.019979 0.035086

62 1 -6.085876 -3.509635 0.942634

63 1 -6.085333 -3.609385 -0.811135

39

64 1 -4.626783 -3.032510 0.036853

65 6 -4.087664 -0.326482 -0.095614

66 6 -2.859216 -0.228335 -0.088447

67 6 4.963726 8.730921 -0.080842

68 6 5.035517 7.350020 -0.074382

69 6 3.889651 6.547990 -0.098052

70 6 3.957210 10.710317 -0.118715

71 6 5.360461 10.960991 -0.071402

72 6 5.994802 9.720188 -0.047076

73 1 6.008314 6.872059 -0.044926

74 6 3.747909 5.144457 -0.087352

75 6 1.695608 6.156524 -0.143814

76 6 2.357368 4.894941 -0.115885

77 7 3.726579 9.382438 -0.124466

78 7 2.618416 7.135204 -0.133021

79 5 2.337695 8.672870 -0.163967

80 9 1.579196 9.041214 0.947836

81 9 1.657858 9.004620 -1.339007

82 6 4.834234 4.118960 -0.059880

83 1 4.865689 3.555477 -0.999784

84 1 5.817950 4.567532 0.094045

85 1 4.663476 3.392277 0.741369

86 6 7.465170 9.447566 0.023325

87 1 7.837198 9.535082 1.051238

88 1 7.711051 8.443370 -0.330602

89 1 8.028180 10.162823 -0.583885

90 6 2.844175 11.704542 -0.149139

91 1 2.115206 11.436682 -0.918232

92 1 2.311905 11.712631 0.808453

93 1 3.220495 12.709619 -0.343686

94 6 0.228576 6.418645 -0.178873

95 1 -0.074513 7.014581 0.687412

40

96 1 -0.035550 6.995501 -1.070517

97 1 -0.324859 5.478758 -0.181215

98 6 1.721264 3.635918 -0.108303

99 6 1.179528 2.544442 -0.099103

100 6 -0.657124 -1.285982 -0.043544

101 6 -1.458675 -0.120712 -0.077767

102 6 -0.845803 1.154299 -0.099094

103 6 0.551106 1.267793 -0.084507

104 6 1.336512 0.095946 -0.052374

105 6 0.740504 -1.183007 -0.032126

106 1 -1.129745 -2.260585 -0.027385

107 1 -1.463016 2.044200 -0.124261

108 1 2.416909 0.179710 -0.042490

109 6 7.812899 -11.273987 0.200979

110 1 8.705869 -11.088497 0.809421

111 1 7.279863 -12.095884 0.692026

112 6 8.245408 -11.725552 -1.206712

113 1 8.818281 -10.943252 -1.714825

114 1 8.872342 -12.621245 -1.150610

115 1 7.375547 -11.958161 -1.829034

116 6 6.008777 12.317351 -0.023638

117 1 5.444967 13.019800 -0.648683

118 1 7.007924 12.253498 -0.469164

119 6 6.128702 12.892786 1.400018

120 1 6.610200 13.875782 1.381322

121 1 5.144037 13.007293 1.864502

122 1 6.724290 12.234978 2.040821

123 6 -13.709955 -1.098325 -0.093756

124 1 -14.166086 -0.298734 -0.689533

125 1 -13.997488 -2.036610 -0.582307

126 6 -14.309044 -1.067092 1.325487

127 1 -14.076667 -0.122800 1.828163

41

128 1 -15.398405 -1.175535 1.292124

129 1 -13.905638 -1.878310 1.939964

polymer material and its related chromophores supporting ... · singlet excited electronic states....

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